Dichloroquinoline derivatives for use as herbicides

ABSTRACT

Dichloroquinoline derivatives of the formula ##STR1## are prepared as described, and are used as herbicides.

The present invention relates to dichloroquinoline derivatives, aprocess for their preparation, herbicides containing these compounds andmethods of controlling undesirable plant growth using these compounds.

Quinoline compounds, eg. 7-chloroquinoline (German Laid-Open ApplicationDOS No. 2,322,143) and 4-chloro-3-nitroquinoline (U.S. Pat. No.2,661,276), have been disclosed as herbicides which have selective,properties and can also be used for total vegetation control. Thedifferent levels of action are remarkable; introduction of the carboxylgroup, for example as in 7-chloro-4-hydroxyquinoline-2-carboxylic acid,leads to a substantial loss in activity in comparison with7-chloro-4-hydroxyquinoline and other derivatives of this type (U.S.Pat. No. 2,661,276).

We have found that dischloroquinoline derivatives of the formula I##STR2## where X is chlorine in the 5-, 6- or 7-position, Y is oxygen,sulfur, hydroxyimino, two hydrogen atoms, two chlorine atoms or═N--A--B, where A is a direct bond or CH₂ and B is a phenyl or pyridineradical which is unsubstituted or substituted by chlorine, nitro,methyl, trifluoromethyl or methoxy, and R¹ is hydrogen, halogen, cyanoor --NR² R³, where R² and R³ are identical or different and each ishydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkenyl, C₁ -C₆ -hydroxyalkyl, formyl,cyclohexyl, phenyl or pyridinyl, or R² and R³ together are (CH₂)₄ or(CH₂)₅, it being possible for one CH₂ group to be replaced by oxygen,nitrogen or N--CH₃, or R¹ is COOH or OM, where M is a metal of maingroup 1 or 2 of the Periodic Table, hydrogen, C₁ -C₈ -alkyl, phenylwhich is unsubstituted or substituted by halogen, nitro, C₁ -C₄ -alkylor trihalomethyl, or H₂ N.sup.⊕ R² R³, where R² and R³ have the abovemeanings, or Y and R¹, together with the carbon atom, are nitrile, havea good herbicidal action.

Preferably, in formula I, X is chlorine in the 7-position, R¹ ishydrogen, OH, ONa, ON.sup.⊕ H₂ (CH₃)₂ or NHCHO and Y is oxygen, twochlorine or hydrogen atoms or ##STR3##

The novel compounds are obtained when a compound of the formula II##STR4## where X has the above meanings, is chlorinated at from 140° to190° C. using a free radical initiator and with exclusion of light, and,if desired, the resulting compound of the formula III ##STR5## where Xhas the same meanings as above and R is chloromethyl, dichloromethyl ortrichloromethyl, is converted into a compound of the formula I where R¹--C═Y is other than R.

The 8-methylguinolines used in the process according to the inventionare known compounds. Their preparation has been described, for example,by Bradford in J. Chem. Soc. 1947, 437, and by Irving in J. Amer. Chem.Soc. 72, (1950), 4059.

Prior art chlorination of N-containing heterocyclic compounds iseffected in acetic acid or sulfuric acid (cf. Houben-Weyl, Volume V/3,pages 725 f, Georg Thieme Verlag, 1962), and, in the case of side-chainchlorination, under UV light (cf. Houben-Weyl, Volume V/3, page 747,Georg Thieme Verlag, 1962).

Surprisingly, in the case of 8-methylquinolines, it is possiblesimultaneously to effect specific nuclear chlorination in the 3-positionas well as side-chain chlorination by suitable choice of the reactionparameters. With the chosen reaction parameters and by adjusting theamount of chlorine and the chlorination time, the reaction can beconducted exactly, permitting selective preparation of the chloromethyl,dichloromethyl or trichloromethyl compound.

The chlorination is carried out in an inert solvent, eg. adichlorobenzene or trichlorobenzene, in the presence of a free radicalinitiator, eg. azoisobutyronitrile or benzoyl peroxide, with exclusionof light, at from 140° to 190° C., preferably from 150° to 160° C.Nuclear chlorination no longer takes place above 190° C.

The compounds where Y is oxygen are obtained by treating thecorresponding dichloro compound with a strong acid, such as concentratedsulfuric acid or concentrated hydrochloric acid, at from 50° to 150° C.

The compounds where Y is sulfur are obtained by reacting thecorresponding nitrile with hydrogen sulfide in a basic solvent,preferably pyridine.

The compounds where Y is hydroxyimino are obtained by heating thecorresponding aldehyde with hydroxylamine at from 50° to 150° C. Ifhydroxylamine hydrochloride or hydroxylammomium sulfate is used insteadof free hydroxylamine, a base must be added. Suitable bases are sodiumcarbonate, sodium bicarbonate, sodium hydroxide solution and thecorresponding potassium compounds.

The compounds where Y is ═N--A--B are obtained from the correspondingaldehyde and the compound H₂ N--A--B by heating at from 50° to 150° C.in a solvent, such as an alcohol or open-chain or cyclic aliphaticether.

The compounds where R¹ is cyano are obtained by reacting thecorresponding chloro compound with potassium cyanide or sodium cyanidein a solvent, such as dimethylformamide or dimethylsulfoxide, at from100° to 200° C. in the presence of a little potassium iodide.

The compounds where R¹ is NR² R³ are obtained by reacting thecorresponding amide with the corresponding chloro compound at from 30°to 100° C. in the presence or absence of a solvent, such as an alcohol,an ether, or dimethylsulfoxide.

The ammonium compounds are obtained by reacting the correspondingcarboxylic acid with an amine, for example in an alcohol ordimethylformamide or dimethylsulfoxide, at from 50° to 150° C.

The compounds where R¹ is COOH are obtained, for example, by hydrolyzingthe corresponding nitrile with concentrated sulfuric acid.

The compounds where R¹ is OH are obtained by reacting the correspondingchloro compound with sodium hydroxide or potassium hydroxide.

The Examples which follow illustrate the preparation of the novelcompounds:

EXAMPLE 1

89 parts of 7-chloro-8-methylquinoline and 0.5 part ofazobisisobutyronitrile were introduced into 500 parts of dichlorobenzeneand the mixture was heated to 140° C. Introduction of 80 parts ofchlorine was started at this temperature the temperature being increasedto 160° C. during this operation. After the addition of chlorine, thesolution was flushed with nitrogen, most of the solvent was distilledoff and the precipitated solid was filtered off with suction and washedwith petroleum ether. 113 parts of 3,7-dichloro-8-chloromethylquinolineof melting point 129° C. were obtained. The yield corresponds to 93% oftheory.

EXAMPLE 2

177 parts of 7-chloro-8-methylquinoline and 1 part ofazobisisobutyronitrile were introduced into 1,000 parts ofdichlorobenzene and the mixture was heated to 140° C. Introduction of250 parts of chlorine started at this temperature. The temperature wasincreased to 175° C. When the reaction has ended, the solution wasflushed with nitrogen and then most of the solvent was distilled off andthe precipitated solid was filtered off with suction and washed withpetroleum ether. 255 parts of 3,7-dichloro-8-dichloromethylquinoline ofmelting point 154° C. were obtained. The yield corresponds to 80% oftheory.

EXAMPLE 3

35 parts of 6-chloro-8-methylquinoline and 0.5 part ofazobisisobutyronitrile in 200 parts of dichlorobenzene were heated to140° C. Introduction of 70-90 parts of chlorine was started at thistemperature, whilst the temperature was increased to 180° C. When thereaction had ended, the solution was flushed with nitrogen, the solventwas distilled off and the residue was recrystallized from naphtha. 52parts of 3,6-dichloro-8-trichloromethylquinoline of melting point 198°C. were obtained. The yield corresponds to 82% of theory.

EXAMPLE 4

56 parts of 3,7-dichloro-8-dichloromethylquinoline in 250 parts of 90%strength sulfuric acid were stirred at 100° C. for 6 hours. Aftercooling, the solution was poured onto ice and the precipitated solid wasfiltered off with suction, washed neutral with water and dried. 195parts of 3,7-dichloroquinoline-8-carbaldehyde of melting point 208° C.were obtained. The yield corresponds to 87% of theory.

EXAMPLE 5

22.6 parts of 3,7-dichloroquinoline-8-carbaldehyde (Example 4) weredissolved in 300 parts of alcohol. 10.6 parts of sodium carbonate and6.9 parts of hydroxylammonium chloride were added to this solution andthe suspension was refluxed for 1 hour. 1,000 parts of water were thenadded and the precipitated solid was filtered off and dried. 23 parts of3,7-dichloro-8-hydroxyiminoquinoline of melting point 202° C. wereobtained. The yield corresponds to 96% of theory.

EXAMPLE 6

24.6 parts of 3,7-dichloro-8-chloromethylquinoline and 30 parts ofdiethylamine were stirred at 55° C. for 6 hours. Water was added and thesolid was filtered off with suction and dried. 25 parts of3,7-dichloro-8-diethylaminomethylquinoline of melting point 54° C. wereobtained. The yield corresponds to 89% of theory.

EXAMPLE 7

24.6 parts of 3,7-dichloro-8-chloromethylquinoline (Example 1) and 15parts of sodium p-chlorophenate in 200 parts of dimethylformamide werestirred at 100° C. for 10 hours. The solvent was distilled off, waterwas added to the residue and the solid was filtered off with suction,dried and recrystallized from a suitable solvent. 32 parts of3,7-dichloro-8-p-chlorophenoxymethylquinoline of melting point 110° C.were obtained. The yield corresponds to 95% of theory.

EXAMPLE 8

49 parts of 3,7-dichloro-8-chloromethylquinoline (Example 1), 13 partsof potassium cyanide and 0.1 part of potassium iodide in 300 parts ofdimethylformamide were heated at 150° C. for 4 hours. Water was added tothe reaction solution and the precipitated product was filtered off withsuction and recrystallized from methylglycol. 32 parts of3,7-dichloro-8-cyanomethylquinoline of melting point 152° C. wereobtained. The yield corresponds to 67% of theory.

EXAMPLE 9

28.1 parts of 3,7-dichloro-8-chloromethylquinoline (Example 1), 6.95parts of hydroxylamine hydrochloride and 13.6 parts of sodium formate in200 ml of formic acid and 60 ml of water were stirred at 100° C. for 12hours. The reaction solution was poured onto ice and the precipitatedsolid was filtered off with suction, washed neutral with water anddried. 19 parts of 3,7-dichloro-8-cyanoquinoline of melting point 222°C. were obtained. The yield corresponds to 78.5% of theory.

EXAMPLE 10

200 parts of 3,7-dichloro-8-cyanoquinoline (Example 9) in 2,600 parts of65% strength sulfuric acid were stirred at 140° C. for 20 hours. Thecooled solution was poured onto ice, the precipitated solid was filteredoff with suction, dried, and taken up in dimethylformamide, activecharcoal was added, the mixture was filtered, water was added to thefiltrate and the solid was filtered off with suction, washed with waterand dried. 200 parts of 3,7-dichloroquinoline-8-carboxylic acid ofmelting point 272° C. were obtained. The yield corresponds to 92% oftheory.

EXAMPLE 11

20 parts of 3,5-dichloroquinoline-8-carbaldehyde (prepared by a methodsimilar to that in Example 4) and 14.6 parts of 2,4-dichloroaniline in300 parts of alcohol were refluxed for 3 hours. The solution was cooledand the precipitated product was filtered off with suction andrecrystallized from methylglycol. 30 g of3,5-dichloro-8-(2,4-dichlorophenyliminomethyl)-quinoline of meltingpoint 156° C. were obtained. The yield corresponds to 90% of theory.

EXAMPLE 12

24.6 parts of 3,7-dichloro-8-chloromethylquinoline (Example 1) in 300parts of formamide were refluxed for 5 hours. Water was added and thesolid was filtered off with suction and recrystallized from methanol. 23parts of 3,7-dichloro-8-formylaminomethylquinoline of melting point 110°C. were obtained. The yield corresponds to 94% of theory.

EXAMPLE 13

22 parts of 3,6-dichloro-8-cyanoquinoline (prepared by a method similarto that in Example 8) in 80 parts of triethylamine and 80 parts ofpyridine were heated at 40° C., and H₂ S gas was slowly passed in for 4hours. Water was then added and the solid was filtered off with suction,washed with water and acetone and recrystallized from ethyl acetate. 17parts of 3,6-dichloroquinoline-8-thiocarboxylic acid amide of meltingpoint 226° C. were obtained. The yield corresponds to 66% of theory.

The following compounds were prepared or can be prepared analogously toExamples 1 to 12:

    __________________________________________________________________________    Ex.                                                                              X  Y                R.sup.1      M.p. [°C.]                         __________________________________________________________________________    14 7-Cl                                                                             N(2-pyridyl)     H            104                                       15 7-Cl                                                                             O                                                                                               ##STR6##    206                                         16                                                                             7-Cl                                                                             O                OC.sub.3 H.sub.7                                                                           112                                       17 7-Cl                                                                             H,H              O(4-CH.sub.3C.sub.6 H.sub.4)                                                               88-90                                     18 7-Cl                                                                             H,H              O(2,4-DiNO.sub.2C.sub.6 H.sub.3)                                                           144                                       19 7-Cl                                                                             H,H              O(2,4-DiClC.sub.6 H.sub.3)                                                                 134                                       20 7-Cl                                                                             H,H              O(4-CH.sub.3 OC.sub.6 H.sub.4)                                                             155                                       21 7-Cl                                                                             H,H              O(2-NO.sub.2C.sub.6 H.sub.4)                                                               167-168                                   22 7-Cl                                                                             H,H              O(3-NO.sub.2C.sub.6 H.sub.4)                                                               140-142                                   23 7-Cl                                                                             H,H              O(C.sub.6 H.sub.5)                                                                         --                                        24 7-Cl                                                                             H,H              O(4-BrC.sub.6 H.sub.4)                                                                     --                                        25 7-Cl                                                                             H,H              O(4-CCl.sub.3C.sub.6 H.sub.4)                                                              --                                        26 7-Cl                                                                             H,H              OC.sub.4 H.sub.9                                                                           --                                        27 7-Cl                                                                             H,H              OC.sub.5 H.sub.11                                                                          --                                        28 7-Cl                                                                             H,H              O.sub.6 H.sub.13                                                                           --                                        29 7-Cl                                                                             H,H              OCH.sub.3    78                                        30 7-Cl                                                                             H,H              OC.sub.2 H.sub.5                                                                           --                                        31 7-Cl                                                                             H,H              Oiso-C.sub.3 H.sub.7                                                                       --                                        32 7-Cl                                                                             O                N(C.sub.2 H.sub.5).sub.2                                                                   145                                                                           (.3H.sub.2 O)                               33                                                                             7-Cl                                                                             O                                                                                               ##STR7##    223                                         34                                                                             7-Cl                                                                             O                NH.sub.2     238                                       35 7-Cl                                                                             O                N(CH.sub.2CH.sub.2 OH).sub.2                                                               --                                        36 7-Cl                                                                             O                N(CH.sub.2CHCH.sub.2).sub.2                                                                --                                          37                                                                             7-Cl                                                                             O                                                                                               ##STR8##                                                38                                                                             7-Cl                                                                             O                                                                                               ##STR9##    --                                          39                                                                             7-Cl                                                                             O                Npiperidinyl --                                        40 7-Cl                                                                             O                Npyrrolidinyl                                                                              --                                        41 7-Cl                                                                             O                NHCH.sub.3   --                                        42 7-Cl                                                                             O                NHC.sub.6 H.sub.5                                                                          --                                        43 7-Cl                                                                             S                NH.sub.2     --                                        44 7-Cl                                                                             S                N(CH.sub.2 CH.sub.2 OH).sub.2                                                              --                                          45                                                                             7-Cl                                                                             H,H                                                                                             ##STR10##   82                                          46                                                                             7-Cl                                                                             H,H              NH(2-pyridyl)                                                                              > 270                                                                         (.HCl)                                    47 7-Cl                                                                             H,H              NHCH.sub.2CHCH.sub.2                                                                       198                                                                           (.HCl)                                       48                                                                            7-Cl                                                                             H,H                                                                                             ##STR11##   230  (.HCl)                                 49                                                                             7-Cl                                                                             H,H              N(C.sub.3 H.sub.7).sub.2                                                                   84                                                                            (.HCl)                                    50 7-Cl                                                                             H,H              N(Cyclohexyl).sub.2                                                                        >280                                                                          (.HCl)                                    51 7-Cl                                                                             H,H              NHC.sub.6 H.sub.13                                                                         110                                                                           (.HCl)                                    52 7-Cl                                                                             H,H              Npyrrolidinyl                                                                              260                                                                           (.HCl)                                    53 7-Cl                                                                             H,H              Npiperidinyl >260                                                                          (.HCl)                                      54                                                                             7-Cl                                                                             H,H                                                                                             ##STR12##   117                                         55                                                                             7-Cl                                                                             H,H                                                                                             ##STR13##   90                                          56                                                                             7-Cl                                                                             O                OCH.sub.3    102                                       57 7-Cl                                                                             O                OC.sub.2 H.sub.5                                                                           109                                       58 7-Cl                                                                             O                OC.sub.4 H.sub.9                                                                           --                                        59 7-Cl                                                                             O                OC.sub.5 H.sub.11                                                                          --                                        60 7-Cl                                                                             O                OC.sub.6 H.sub.13                                                                          --                                        61 6-Cl                                                                             N(4-ClC.sub.6 H.sub.4)                                                                         H            180                                       62 6-Cl                                                                             N (2,4-DiClC.sub.6 H.sub.4)                                                                    H            176                                       63 6-Cl                                                                             N(2,5-DiCH.sub.3C.sub.6 H.sub.3)                                                               H            140                                       64 5-Cl                                                                             N(3CF.sub.3C.sub.6 H.sub.4)                                                                    H            160                                       65 6-Cl                                                                             N(2,4-DiCH.sub.3C.sub.6 H.sub.3)                                                               H            130                                       66 5-Cl                                                                             N(2,4-DiCH.sub.3C.sub.6 H.sub.3)                                                               H            120                                         67                                                                             6-Cl                                                                              ##STR14##       H            180                                         68                                                                             5-Cl                                                                             N(4-NO.sub.2C.sub.6 H.sub.4)                                                                   H            260                                       69 7-Cl                                                                             NCH.sub.2(2,6-DiCH.sub.3C.sub.6 H.sub.3)                                                       H            154                                       70 6-Cl                                                                             N(4-CH.sub.3 OC.sub.6 H.sub.4)                                                                 H            180                                       71 6-Cl                                                                             Cl, Cl           H            134                                       72 6-Cl                                                                             O                OH           238                                                              ⊖⊕                                         73 5-Cl                                                                             O                ONa          >300                                                             ⊖⊕                                         74 7-Cl                                                                             O                ONa          >300                                                             ⊖⊕                                         75 7-Cl                                                                             O                ONH.sub.2 (CH.sub.3).sub.2                                                                 180                                       76 5-Cl                                                                             Cl, Cl           H            130                                       77 5-Cl                                                                             O                H            170                                       78 7-Cl                                                                             H, H             COOH         210                                       79 5-Cl                                                                             O                OH           200                                                              ⊖ ⊕                                        80 5-Cl                                                                             O                ONH.sub.2 (CH.sub.3).sub.2                                                                 >270                                      81 5-Cl                                                                             O                Cl           --                                        82 6-Cl                                                                             O                Cl           75                                        83 5-Cl                                                                             O                OCH.sub.3    --                                        84 5-Cl                                                                             O                OC.sub.4 H.sub.9                                                                           --                                        85 5-Cl                                                                             O                OC.sub.6 H.sub.13                                                                          --                                        86 7-Cl                                                                             O                OCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                               --                                        87 7-Cl                                                                             Cl, Cl           Cl           135                                       88 7-Cl                                                                             O                Cl           91                                                               ⊖⊕                                         89 6-Cl                                                                             O                ONa          >300                                      90 6-Cl                                                                             N(3-CF.sub.3C.sub.6 H.sub.4)                                                                   H            103                                       91 6-Cl                                                                             O                OCH.sub.3    --                                        92 6-Cl                                                                             O                OC.sub.5 H.sub.11                                                                          --                                        93 6-Cl                                                                             O                OC.sub.3 H.sub.7                                                                           --                                        94 6-Cl                                                                             O                N(C.sub.2 H.sub.5).sub.2                                                                   --                                          95                                                                             5-Cl                                                                             O                                                                                               ##STR15##   --                                          96                                                                             5-Cl                                                                             O                                                                                               ##STR16##   --                                           97                                                                            5-Cl                                                                             O                N(CH.sub.3).sub.2                                                                          --                                        98 6-Cl                                                                             O                Npyrrolidinyl                                                                              --                                        99 6-Cl                N            150                                       100                                                                              5-Cl                N            174                                       __________________________________________________________________________

The influence of various representative of the novel quinolinederivatives on the growth of unwanted and crop plants is demonstrated inthe greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³,and which were filled with a sandy loam containing about 1.5% humus. Inthe case of Galium aparine, and of rice which was cultivated for thepostemergence treatment, peat was added to ensure troublefree growth.The seeds of the test plants were sown shallow, and separately,according to species.

In the preemergence treatment, the active ingredients were thenimmediately applied to the surface of the soil as a suspension oremulsion in water by spraying through finely distributing nozzles. Theamount of active ingredient applied in this treatment varied, and waseither 0.5, 1.0 or 2.0 kg/ha.

After the agents had been applied, the vessels were lightlysprinkler-irrigated to induce germination and growth. Transparentplastic covers were then placed on the vessels until the plants hadtaken root. The cover ensured uniform germination of the plants, insofaras this was not impaired by the chemicals.

For the postmergence treatment, the plants were first grown in thevessels to a height of from 3 to 15 cm, depending on growth form, beforebeing treated. For this treatment, either plants which had been sowndirectly in the pots and grown there were selected, or plants which hadbeen grown separately as seedlings and transplanted to the experimentvessels a few days before treatment. The amounts of active ingredientapplied in this treatment also varied, and were either 1.0, 2.0 or 4.0kg/ha. No cover was placed on the vessels in this treatment.

The pots were set up in the greenhouse--species from warmer areas atfrom 20° to 30° C., and species from moderate climates at 15° to 25° C.The experiments were run for from 3 to 4 weeks. During this period, theplants were tended and their reactions to the various treatmentsassessed. The scale used for assessment was 0 to 100, 0 denoting nodamage or normal emergence, and 100 denoting nonemergence or completedestruction of at least the visible plant parts.

The prior art compounds 7-chloroquinoline (A; German Laid-OpenApplication DOS No. 2,322,143) and7-chloro-4-hydroxyquinoline-2-carboxylic acid (B; U.S. Pat. No.2,661,276) were used at a rate of 1.0 kg/ha under the same pre- andpostemergence conditions for comparison purposes.

The results show that the compounds have a considerable herbicidalaction on both pre- and postemergence application, and are tolerated asselective agents by various crop plants or cause at most only slightdamage.

If certain crop plants tolerate, on leaf treatment, the activeingredients less well, application techniques may be used in which theagents are sprayed from suitable equipment in such a manner that theleaves of sensitive crop plants are if possible not touched, and theagents reach the soil or the unwanted plants growing beneath the cropplants (post-directed, lay-by treatment).

In view of the many application methods possible, the herbicidesaccording to the invention may be used in a very wide range of crops forremoving unwanted plants. The application rates may vary between 0.05and 10 kg of active ingredient per hectare and more.

The following crop plants may be mentioned by way of example:

    ______________________________________                                        Botanical name     Common name                                                ______________________________________                                        Abutilon theophrasti                                                                             velvetleaf                                                 Allium cepa        onions                                                     Ananas comosus     pineapples                                                 Arachis hypogaea   peanuts (groundnuts)                                       Asparagus officinalis                                                                            asparagus                                                  Avena sativa       oats                                                       Beta vulgaris spp. altissima                                                                     sugarbeets                                                 Beta vulgaris spp. rapa                                                                          fodder beets                                               Beta vulgaris spp. esculenta                                                                     table beets, red beets                                     Brassica napus var. napus                                                                        rape seed                                                  Brassica napus var. napobrassica                                              Brassica napus var. rapa                                                                         turnips                                                    Brassica rapa var. silvestris                                                 Camellia sinensis  tea plants                                                 Carthamus tinctorius                                                                             safflower                                                  Carya illinoinensis                                                                              pecan trees                                                Cirsium arvense    Canada thistle                                             Citrus limon       lemons                                                     Citrus maxima      grapefruits                                                Citrus reticulata  mandarins                                                  Citrus sinensis    orange trees                                               Coffea arabica (Coffea canephora,                                                                coffee plants                                              Coffea liberica)                                                              Cucumis melo       melons                                                     Cucumis sativus    cucumbers                                                  Cynodon dactylon   Bermudagrass in turf and                                                      lawns                                                      Daucus carota      carrots                                                    Elais guineensis   oil palms                                                  Fragaria vesca     strawberries                                               Glycine max        soybeans                                                   Gossypium hirsutum cotton                                                     (Gossypium arboreum                                                           Gossypium herbaceum                                                           Gossypium vitifolium)                                                         Helianthus annuus  sunflowers                                                 Helianthus tuberosus                                                          Hevea brasiliensis rubber plants                                              Hordeum vulgare    barley                                                     Humulus lupulus    hops                                                       Ipomoea batatas    sweet potatoes                                             Juglans regia      walnut trees                                               Lactuca sativa     lettuce                                                    Lens culinaris     lentils                                                    Linum usitatissimum                                                                              flax                                                       Lycopersicon lycopersicum                                                                        tomatoes                                                   Malus spp.         apple trees                                                Manihot esculenta  cassava                                                    Medicago sativa    alfalfa (lucerne)                                          Mentha piperita    peppermint                                                 Musa spp.          banana plants                                              Nicothiana tabacum tobacco                                                    (N. rustica)                                                                  Olea europaea      olive trees                                                Oryza sativa       rice                                                       Panicum miliaceum                                                             Phaseolus lunatus  limabeans                                                  Phaseolus mungo    mungbeans                                                  Phaseolus vulgaris snapbeans, green beans,                                                       dry beans                                                  Pennisetum glaucum                                                            Petroselinum crispum                                                                             parsley                                                    spp. tuberosum                                                                Picea abies        Norway spruce                                              Abies alba         fir trees                                                  Pinus spp.         pine trees                                                 Pisum sativum      English peas                                               Prunus avium       cherry trees                                               Prunus domestica   plum trees                                                 Prunus dulcis      almond trees                                               Prunus persica     peach trees                                                Pyrus communis     pear trees                                                 Ribes sylvestre    redcurrants                                                Ribes uva-crispa   gooseberries                                               Ricinus communis   castor-oil plants                                          Saccharum officinarum                                                                            sugar cane                                                 Secale cereale     rye                                                        Sesamum indicum    sesame                                                     Solanum tuberosum  Irish potatoes                                             Sorghum bicolor (s. vulgare)                                                                     sorghum                                                    Sorghum dochna                                                                Spinacia oleracea  spinach                                                     Theobroma cacao   cacao plants                                               Trifolium pratense red clover                                                 Triticum aestivum  wheat                                                      Vaccinium corymbosum                                                                             blueberries                                                Vaccinium vitis-idaea                                                                            cranberries                                                Vicia faba         tick beans                                                 Vigna sinensis (V. unguiculata)                                                                  cow peas                                                   Vitis vinifera     grapes                                                     Zea mays           Indian corn, sweet corn, maize                             ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects,the novel substituted quinoline derivatives may be mixed amongthemselves, or mixed and applied together with numerous representativesof other herbicidal or growth-regulating active ingredient groups.Examples of suitable mixture components are diazines, 4H-3,1-benzoxazinederivatives, benzothiadiazinones, 2,6-dinitroanilines,N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines,amides, ureas, diphenyl ethers, triazinones, uracils, benzofuranderivatives, cyclohexane-1,3-dione derivatives, etc. A number of activeingredients which, when combined with the new compounds, give mixturesuseful for widely varying applications are given below by way ofexample:

5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone

5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone

5-amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone

5-amino-4-bromo-2-cyclohexyl-3(2H)-pyridazinone

5-methylamino-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-methylamino-4-chloro-2-(3-α,α,β,β-tetrafluoroethoxyphenyl)-3(2H)-pyridazinone

5-dimethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone

4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone

4,5-dimethoxy-2-cyclohexyl-3(2H)-pyridazinone

4,5-dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-amino-4-bromo-2(3-methylphenyl)-3(2H)-pyridazinone

3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide andsalts

3-(1-methylethyl)-8-chloro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

3-(1-methylethyl)-8-fluoro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

3-(1-methylethyl)-8-methyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

1-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-methoxymethyl-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-methoxymethyl-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-methyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-azidomethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

3-(1-methylethyl)-1H-pyridino-[3,2-e]-2,1,3-thiadiazin-(4)-one-2.2-dioxide

N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline

N-(1-methylethyl)-N-ethyl-2,6-dinitro-4-trifluoromethylaniline

N-n-propyl-N-β-chloroethyl-2,6-dinitro-4-trifluoromethyl-aniline

N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethylaniline

N-bis-(n-propyl)-2,6-dinitro-3-amino-4-trifluoromethylaniline

N-bis-(n-propyl)-2,6-dinitro-4-methylaniline

N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline

N-bis-(n-propyl)-2,6-dinitro-4-aminosulfonylaniline

bis-(β-chloroethyl)-2,6-dinitro-4-methylaniline

N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline

3,4-dichlorobenzyl N-methylcarbamate

2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate

isopropyl N-phenylcarbamate

3-methoxyprop-2-yl N-3-fluorophenylcarbamate

isopropyl N-3-chlorophenylcarbamate

but-1-yn-3-yl N-3-chlorophenylcarbamate

4-chlorobut-2-yn-1-yl N-3-chlorophenylcarbamate

methyl N-3,4-dichlorophenylcarbamate

methyl N-(4-aminobenzenesulfonyl)-carbamate

O-(N-phenylcarbamoyl)-propanone oxime

N-ethyl-2-(phenylcarbamoyl)-oxypropionic acid amide

3'-N-isopropylcarbamoyloxypropionanilide

ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-methyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate

isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamoyloxy)-carbamate

methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate

ethyl-N-[3-N'-(3-chloro-4-fluorophenylcarbamoxyloxy)-phenyl]-carbamate

ethyl-N-[3-N'-(3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate

methyl-N-[3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate

methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylcarbamate

ethyl N-3-(2'-methylphenoxycarbonylamino)-phenylcarbamate

methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate

methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiolcarbamate

methyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate

p-chlorobenzyl N,N-diethylthiolcarbamate

ethyl N,N-di-n-propylthiolcarbamate

n-propyl N,N-di-n-propylthiolcarbamate

2,3-dichloroallyl N,N-diisopropylthiolcarbamate

2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate

3-methyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate

3-ethyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate

ethyl N,N-di-sec.-butylthiolcarbamate

benzyl N,N-di-sec.-butylthiolcarbamate

ethyl N-ethyl-N-cyclohexylthiolcarbamate

ethyl N-ethyl-N-bicyclo-[2.2.1]-heptylthiolcarbamate

S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidino)-1-carbothiolate

S-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate

S-ethylhexahydro-1-H-azepine-1-carbothiolate

S-benzyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate

S-benzyl-(2,3-dimethylhexahydro-1-H-azepine-1)-carbothiolate

S-ethyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate

n-propyl N-ethyl-N-n-butylthiolcarbamate

2-chloroallyl N,N-dimethyldithiocarbamate

N-methyldithiocarbamic acid, sodium salt

trichloroacetic acid, sodium salt

α,α-dichloropropionic acid, sodium salt

α,α-dichlorobutyric acid, sodium salt

α,α-β,β-tetrafluoropropionic acid, sodium salt

α-methyl-α,β-dichloropropionic acid, sodium salt

methylα-chloro-β-(4-chlorophenyl)-propionate

methylα,β-dichloro-β-phenylpropionate

benzamido oxyacetic acid

2,3,5-triiodobenzoic acid (salts, esters, amides)

2,3,6-trichlorobenzoic acid (salts, esters, amides)

2,3,5,6-tetrachlorobenzoic acid (salts, esters, amides)

2-methoxy-3,6-dichlorobenzoic acid (salts, esters, amides)

2-methoxy-3,5,6-trichlorobenzoic acid (salts, esters, amides)

3-amino-2,5,6-trichlorobenzoic acid (salts, esters, amides)

O,S-dimethyltetrachlorothioterephthalate

dimethyl-2,3,5,6-tetrachloroterephthalate

disodium 3,6-endoxohexahydrophthalate

4-amino-3,5,6-trichloropicolinic acid (salts)

ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate

isobutyl 2-[4-(4'-chlorophenoxy]-propionate

methyl 2-[4-(2',4'-dichlorophenoxy)-phenoxy]-propionate

methyl 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-propionate

2-[4-(2'-chloro-4'-trifluorophenoxy)-phenoxy ]-propionic acid, sodiumsalt

2-[4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt

ethyl 2-(N-benzoyl-3,4-dichlorophenylamino)-propionate

methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate

isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-chloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine

2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-1,3,5-triazine

2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1,3,5-triazine

2-chloro-4,6-bisethylamino-1,3,5-triazine

2-chloro-4,6-bisisopropylamino-1,3,5-triazine

2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine

2-azido-4-methylamino-6-isopropylamino-1,3,5-triazine

2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine

2-methylthio-4,6-bisethylamino-1,3,5-triazine

2-methylthio-4,6-bisisopropylamino-1,3,5-triazine

2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-methoxy-4,6-bisethylamino-1,3,5-triazine

2-methoxy-4,6-bisisopropylamino-1,3,5-triazine

4-amino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one

4-amino-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one

4-isobutylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one

1-methyl-3-cyclohexyl-6-dimethylamino-1,3,5-triazin- 2,4-dione

3-tert.butyl-5-chloro-6-methyluracil

3-tert.butyl-5-bromo-6-methyluracil

3-isopropyl-5-bromo-6-methyluracil

3-sec.butyl-5-bromo-6-methyluracil

3-(2-tetrahydropyranyl)-5-chloro-6-methyluracil

3-(2-tetrahydropyranyl)-5,6-trimethyleneuracil

3-cyclohexyl-5,6-trimethyleneuracil

2-methyl-4-(3'-trifluoromethylphenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione

2-methyl-4'-fluorophenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione

3-amino-1,2,4-triazole

1-allyloxy-1-(4-bromophenyl)-2-[1',2',4'-triazolyl-(1')]-ethane (salts)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,3-triazol-1-yl)-butan-2-one

N,N-diallylchloroacetamide

N-isopropyl-2-chloroacetanilide

N-(1-methylpropyn-2-yl)-2-chloroacetanilide

2-methyl-6-ethyl-N-propargyl-2-chloroacetanilide

2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanilide

2-methyl-6-ethyl-N-(2-methoxy-1-methylethyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(4-methoxypyrazol-1-yl-methyl)-2-chloro-acetanilide

2-methyl-6-ethyl-N-(pyrazol-1-yl-methyl)-2-chloracetanilide

2,6-dimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-2-chloro-acetanilide

2,6-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide

2,6-dimethyl-N-isobutoxymethyl-2-chloroacetanilide

2,6-diethyl-N-methoxymethyl-2-chloroacetanilide

2,6-diethyl-N-n-butoxymethyl-2-chloroacetanilide

2,6-diethyl-N-ethoxycarbonylmethyl-2-chloroacetanilide

2,3,6-trimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide

2,3-dimethyl-N-isopropyl-2-chloroacetanilide

2,6-diethyl-N-(propoxyethyl)-2-chloroacetanilide

2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide

2-(α-naphthoxy)-N,N-diethylpropionamide

2,2-diphenyl-N,N-dimethylacetamide

α-(3,4,5-tribromopyrazol-1-yl)-N,N-dimethylopropionamide

N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide

N-1-naphthylphthalamic acid

propionic acid 3,4-dichloroanilide

cyclopropanecarboxylic acid 3,4-dichloroanilide

methacrylic acid 3,4-dichloroanilide

2-methylpentanecarboxylic acid 3,4-dichloroanilide

5-acetamido-2,4-dimethyl-trifluoromethanesulfone anilide

5-acetamido-4-methyl-trifluoromethanesulfone anilide

2-propionylamino-4-methyl-5-chlorothiazole

0-(methylsulfonyl)-glycolic acid N-ethoxymethyl-2,6-dimethylanilide

0-(methylaminosulfonyl)-glycolic acid N-isopropylanilide

0-(isopropylaminosulfonyl)-glycolic acid N-but-1-yn-3-yl-anilide

0-(methylaminosulfonyl)-glycolic acid hexamethyleneamide

2,6-dichlorothiobenzamide

2,6-dichlorobenzonitrile

3,5-dibromo-4-hydroxybenzonitrile (salts)

3,5-diiodo-4-hydroxybenzonitrile (salts)

3,5-dibromo-4-hydroxy-0-2,4-dinitrophenylbenzaldoxime (salts)

3,5-dibromo-4-hydroxy-0-2-cyano-4-nitrophenylbenzaldoxime (salts)

pentachlorophenol, sodium salt

2,4-dichlorophenyl-4'-nitrophenyl ether

2,4,6-trichlorophenyl-4'-nitrophenyl ether

2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether

2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether

2,4-dinitro-4-trifluoromethyl-diphenyl ether

2,4-dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether

2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether

2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether(salts)

2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitro-phenyl ether

2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-(3-tert.butylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-(3-isopropylcarbamoyloxyphenyl)4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-phenyl-3,1-benzoxazinone-(4)

(4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-[5,4,1,0²,6, 0,⁸,11]-dodeca-3,9-diene

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyldimethylaminosulfonate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-(N-methyl-N-acetyl)-aminosulfonate

3,4-dichloro-1,2-benzisothiazole

N-4-chlorophenyl-allylsuccinimide

2-methyl-4,6-dinitrophenol (salts, esters)

2-sec.butyl-4,6-dinitrophenol (salts, esters)

2-sec.butyl-4,6-dinitrophenol acetate

2-tert.butyl-4,6-dinitrophenol acetate

2-tert.butyl-4,6-dinitrophenol (salts)

2-tert.butyl-5-methyl-4,6-dinitrophenol (salts)

2-tert.butyl-5-methyl-4,6-dinitrophenol acetate

2-sec.amyl-4,6-dinitrophenol (salts, esters)

1-(α,α-dmethylbenzyl)3-(4-methylphenyl)-urea

1-phenyl-3-(2-methylcyclohexyl)-urea

1-phenyl-1-benzoyl-3,3-dimethylurea

1-(4-chlorophenyl)-1-benzoyl-3,3-dimethylurea

1-(4-chlorophenyl)-3,3-dimethylurea

1-(4-chlorophenyl)-3-methyl-3-but-1-yn-3yl-urea

1-(3,4-dichlorophenyl)-3,3-dimethylurea

1-(3,4-dichlorophenyl)-1-benzoyl-3,3-dimethylurea

1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea

1-(4-isopropylphenyl)-3,3-dimethylurea

1-(3-trifluoromethylphenyl)-3,3-dimethylurea

1-(α,α,β,β-tetrafluoroethoxyphenyl)-3,3-dimethylurea

1-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea

1-(3-chloro-4-methylphenyl)-3,3-dimethylurea

1-(3-chloro-4-methoxyphenyl)-3,3-dimethylurea

1-(3,5-dichloro-4-methoxyphenyl)-3,3-dimethylurea

1-[4-(4'-chlorophenoxy)-phenyl]-3,3-dimethylurea

1-[4-(4'-methoxyphenoxy)-phenyl]-3,3-dimethylurea

1-cyclooctyl-3,3-dimethylurea

1-(hexahydro-4,7-methanoindan-5yl)-3,3-dimethylurea

1-[1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-dimethylurea

1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea

1-phenyl-3-methyl-3-methoxyurea

1-(4-chlorophenyl)-3-methyl-3-methoxyurea

1-(4-bromophenyl)-3-methyl-3-methoxyurea

1-(3,4-dichlorophenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-methoxyphenyl)3-methyl-3-methoxyurea

1-(3-tert.butylphenyl)-3-methyl-3-methoxyurea

1-(2-benzthiazolyl)-1,3-dimethylurea

1-(2-benzthiazolyl)-3-methylurea

1(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dimethylurea

imidazolidin-2-one-1-carboxylic acid isobutylamide

1,2-dimethyl-3,5-diphenylpyrazolium-methylsulfate

1,2,4-trimethyl-3,5-diphenylpyrazolium-methylsulfate

1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium-methylsulfate

1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-(4-methylphenylsulfonyloxy)-pyrazole

2,3,5-trichloropyridinol-(4)

1-methyl-3-phenyl-5-(3'-trifluoromethylphenyl)-pyridone-(4)

1-methyl-4-phenylpyridinium chloride

1,1-dimethylpyridinium chloride

3-phenyl-4-hydroxy-6-chloropyridazine

1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate)

1,1'-di-(3,5-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridyliumdichloride

1,1'-ethylene-2,2'-dipyridylium dibromide

3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

3-[1-(N-allyloxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

2-[1-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-1,3-dione(salts)

2-[1-(N-allyloxyamino-butylidene]-5,5-dimethylcyclohexane-1,3-dione(salts)

2-[1-(N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione(salts)

2-chlorophenoxyacetic acid (salts, esters, amides)

4-chlorophenoxyacetic acid (salts, esters, amides)

2,4-dichlorophenoxyacetic acid (salts, esters, amides)

2,4,5-trichlorophenoxyacetic acid (salts, esters, amides)

2-methyl-4-chlorophenoxyacetic acid (salts, esters, amides)3,5,6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides)

methyl α-naphthoxyacetate

2-(2-methylphenoxy)-propionic acid (salts, esters, amides)

2-(4-chlorophenoxy)-propionic acid (salts, esters, amides)

2(-b 2,4-dichlorophenoxy)-propionic acid (salts, esters, amides)

2-(2,4,5-trichlorophenoxy)-propionic acid (salts, esters, amides)

2-(2-methyl-4-chlorophenoxy)-propionic acid (salts, esters, amides)

4-(2,4-dichlorophenoxy)-butyric acid (salts, esters, amides)

4-(2-methyl-4-chlorophenoxy)-butyric acid (salts, esters, amides)

cyclohexyl-3-(2,4-dichlorophenoxy)-acrylate

9-hydroxyfluorenecarboxylic acid-(9) (salts, esters)

2,3,6-trichlorophenylacetic acid (salts, esters)

4-chloro-2-oxobenzothiazolin-3-yl-acetic acid (salts, esters)

gibelleric acid (salts)

disodium methylarsonate

monosodium salt of methylarsonic acid

N-phosphonomethyl-glycine (salts)

N,N-bis-(phosphonomethyl)-glycine (salts)

2-chloroethyl 2-chloroethanephosphonate

ammonium-ethyl-carbamoyl-phosphonate

di-n-butyl-1-n-butylamino-cyclohexyl-phosphonate

trithiobutylphosphite

0,0-diisopropyl-5-(2-benzosulfonylaminoethyl)-phosphorodithioate2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide

5-tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazolone-(2)

4,5-dichloro-2-trifluoromethylbenzimidazole (salts)

1,2,3,6-tetrahydropyridazine-3,6-dione (salts)

succinic acid mono-N-dimethylhydrazide (salts)

(2-chloroethyl)-trimethylammonium chloride

(2-methyl-4-phenylsulfonyl)-trifluoromethanesulfone anilide

1,1-dimethyl-4,6-diisopropyl-5-indanyl ethyl ketone

sodium chlorate

ammonium thiocyanate

calcium cyanamide

2-chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitrophenyl ether

1-(4-benzyloxyphenyl)-3-methyl-3-methoxyurea

2-[1-(2,5-dimethylphenyl)-ethylsulfonyl]-pyridine-N-oxide

1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole

3-anilino-4-methoxycarbonyl-5-methylpyrazole

3-tert.butylamino-4-methoxycarbonyl-5-methylpyrazole

N-benzyl-N-isopropyl-trimethylacetamide

methyl 2-[4-(4'-chlorophenoxymethyl)-phenoxy]-propionate

ethyl 2-[4-(5'-bromopyridyl-2-oxy)-phenoxy]-propionate

ethyl 2-[4-(5'-iodopyridyl-2-oxy)-phenoxy]-propionate

n-butyl 2-[4-(5'-iodopyridyl-2-oxy)-phenoxy]-propionate

2-chloro-4-trifluoromethylphenyl-3'-(2-fluoroethoxy)-4'-nitrophenylether

2-chloro-4-trifluoromethylphenyl-3-(ethoxycarbonyl)-methylthio-4-nitrophenylether

2,4,6-trichlorophenyl-3-(ethoxycarbonyl)-methylthio-4-nitrophenyl ether

2-[1-(N-ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1-one(salts)

2-[1-(N-ethoxamino)-butylidene]-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-1-one(salts)

ethyl-4-[4-(4'-trifluoromethyl)-phenoxy]-pentene-2-carboxylate

2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrophenyl ether

2,4-dichlorophenyl-3'-carboxy-4-nitrophenyl ether (salts)

4,5-dimethoxy-2-(3-α,α,β-trifluoro-β-bromoethoxyphenyl)-3-(2H)-pyridazinone

2,4dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl ether

2,3-dihydro-3,3-dimethyl-5-benzofuranyl-ethane sulfonate

N-[4-methoxy-6-methyl-1,3,5-triazin-2-yl-aminocarbonyl]-2-chlorobenzenesulfonamide

1-(3-chloro-4-ethoxyphenyl)-3,3-dimethylurea

ethyl 2-methyl-4-chlorophenoxy-thioacetate

2-chloro-3,5-diiodo-4-acetoxy-pyridine

1-(-4-[2-(4-methylphenyl)-ethoxy]-phenyl)-3-methyl-3-methoxyurea

2,6-dimethyl-N-(pyrazol-1-yl-methylenoxymethyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(pyrazol-1-yl-methylenoxmethyl)-2-chloroacetanilide

1(α-2,4-dichlorophenoxypropionic acid)-3-(0-methylcarbamoyl)-anilide

1-(α-2-bromo-4-chlorophenoxypropionicacid)-3-(0-methylcarbamoyl)-anilide

2-methyl-6-ethyl-N-(pyrazol-1-yl-ethylenoxymethyl)-2-chloroacetanilide

methyl-N-dichlorofluoromethylsulfenyl-(3-(N'-dichlorofluoromethylsulfenyl-N'-phenylcarbamoyl-oxy)-phenyl)-carbamate

methyl-N-dichlorofluoromethylsulfenyl-(3-(N'-dichlorfluoromethylsulfenyl-N'-3-methylphenylcarbamoyl-oxy)-phenyl)-carbamate

N-(pyrazol-1-yl-methyl)-pyrazol-1-yl-acetic acid-2,6-dimethylanilide

N-(pyrazol-1-yl-methyl)-1,2,4-triazol-1-yl-aceticacid-2,6-dimethylanilide

2-(3-trifluoromethylphenyl)-4H-3,1-benzoxazin-4-one

2-(2-thienyl)-4H-3,1-benzoxazin-4-one

It may also be useful to apply the novel compounds, either alone or incombination with other herbicides, in admixture with other cropprotection agents, e.g., agents for combating pests or phytopathogenicfungi or bacteria. The compounds may also be mixed with mineral saltsolutions used to remedy nutritional or trace element deficiencies.Non-phytotoxic oils and oil concentrates may also be added.

In investigations into selective herbicidal action on preemergenceapplication in the greenhouse at a rate of 2.0 kg of active ingredientper hectare, for example the compound of Example 2 had quite a goodherbicidal action and was well to acceptably tolerated by rice,sunflowers and wheat. When this compound was employed postemergence inthe greenhouse for selective weed control (application rate: 2 kg/ha),it also had a considerable herbicidal action and was well or acceptablytolerated by crop plants such as oats, rice, rape and wheat.

In investigations into the herbicidal action on preemergence applicationin the greenhouse at 1.0 kg of active ingredient per hectare, forinstance the compound of Example 4 revealed a good herbicidal action andwas well and usefully tolerated by rape, rice and sorghum as examples ofcrop plants.

Further, the compound for instance of Example 14 exhibited, oninvestigations into the herbicidal action on preemergence application inthe greenhouse at a rate of, for example, 1.0 kg/ha, a good herbicidalaction and a consistently good selectivity in rape, rice and wheat.

The compound of Example 10 also exhibited, on preemergence applicationin the greenhouse at the rate of 1.0 kg/ha used by way of example, avery good herbicidal action on grassy and broadleaved unwanted plants.

The investigations into the herbicidal action on postemergenceapplication in the greenhouse at a rate of 1.0 kg/ha, the compound ofExample 10 also had a very good herbicidal action, combined with an onlyslight inhibition in the growth of crop plants, e.g., rice. The sameactive ingredient is also suitable, depending on the weed species to becombated and accordingly selected application rates, as a selectiveagent in other crops.

When the compound of Example 75 was applied pre- and postemergence at0.5 and 1.0 kg/ha to important unwanted plants, it had a herbicidalaction and was well tolerated by crop plants.

The compound of Example 74, applied postemergence in the greenhouse at1.0 kg/ha, also had a good and selective herbicidal action.

Further, the compound of Example 12 combated, on postemergenceapplication of 2.0 kg/ha, a number of grassy and broadleaved unwantedplants and was well tolerated by crop plants.

In the greenhouse experiments described above, the compound of Example10, on pre- and postemergence application of, for example, 1.0 kg/ha,proved to have a herbicidal action far superior to that of comparativecompounds A and B.

In investigations into the herbicidal action on postemergenceapplication in the greenhouse, compound 16 at 2.0 kg/ha, and compound 1at 4.0 kg/ha had a quite remarkable selective herbicidal action. Whencompounds 16 and 69 were applied preemergence in the greenhouse at arate of 2.0 kg/ha, they exhibited a selective herbicidal action.

In greenhouse experiments with azaleas (Rhododendron simsii), it wasable to be shown that for instance compound 10 regulates the shootgrowth of herbaceous plants and may thus be used, depending on theapplication rate employed, as a growth regulator for such plants or forcombating them.

In the open, compound 10 achieved, when applied preemergence at a rateof 0.5 kg/ha in experiments on small plots (the soil of which was asandy loam having a pH of 6 and containing 1 to 1.5% humus), very goodcontrol of naturally occurring weeds, without damaging rape, winterbarley or Indian corn used as examples of crop plants. The activeingredient was emulsified or suspended in water as vehicle and appliedwith the aid of a plot spray mounted on a tractor. Where no naturalprecipitate fell, the plots were sprinkler-irrigated to ensuregermination and growth of crop plants and weeds. Assessment was carriedout at certain intervals on the 0 to 100 scale.

We claim:
 1. A dichloroquinoline derivative of the formula ##STR17##where X is chlorine in the 5-, 6- or 7 position, Y is oxygen, twohydrogen atoms, two chlorine atoms or ═N--A--B, R¹ is hydrogen, OM or--NR² R³ where Y is oxygen; R¹ is OM or --NR² R³, where Y is twohydrogen atoms; R¹ is hydrogen if Y is two chlorine atoms and R¹ ishydrogen if Y is ═N--A--B, where A is a direct bond or CH₂ and B is aphenyl or pyridine radical which is unsubstituted or substituted bychlorine, nitro, methyl, trifluoromethyl or methoxy, and R¹ is hydrogen,or --NR² R³, where R² and R³ are identical or different and each ishydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkenyl, C₁ -C₆ -hydroxyalkyl, formyl,cyclohexyl, phenyl or pyridinyl, or R² and R³ together are (CH₂)₄,(CH₂)₅, (CH₂ --O--(CH₂).sub. 2 or (CH₂ --N(CH₃)--(CH₂)₂, or R¹ is OM,where M is a metal of main group 1 or 2 of the Periodic Table, hydrogen,C₁ -C₈ -alkyl, phenyl which is unsubstituted or substituted by halogen,nitro, C₁ -C₄ -alkyl or trihalomethyl, or H₂ N.sup.⊕ R² R³, where R² andR³ have the above meanings, or Y and R¹, together with the carbon atom,are nitrile.
 2. A herbicide containing a compound of the formula I asset forth in claim 1 and a solid or liquid carrier.
 3. A process forcombating the growth of unwanted plants, wherein the plants or the soilare treated with a compound of the formula I as set forth in claim
 1. 4.A dichloroquinoline derivative of the formula I as set forth in claim 1,where X is chlorine in the 7-position.
 5. A dichloroquinoline derivativeof the formula I as set forth in claim 1, where X is chlorine in the7-position, Y is oxygen, two hydrogen atoms or ═N--A--B, where A is adirect bond and B is a phenyl or pyridine radical which is unsubstitutedor substituted by chlorine, nitro, methyl, trifluoromethyl or methoxy,and R¹ is hydrogen, --NR² R³, where R² and R³ are identical or differentand each is hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkenyl, C₁ -C₆-hydroxyalkyl, formyl, cyclohexyl, phenyl or pyridinyl, or R¹ is OM,where M is a metal of main group 1 or 2 of the Periodic Table, hydrogen,C₁ -C₈ -alkyl, phenyl which is unsubstituted or substituted by halogen,nitro, C₁ -C₄ -alkyl or trihalomethyl.
 6. A dichloroquinoline derivativeof the formula ##STR18## where X is chlorine in the 7-position, Y is twohydrogen atoms and R¹ is --NR² R³, where R² and R³ are identical ordifferent and each is C₁ -C₆ -alkyl or phenyl.
 7. A dichloroquinolinederivative of the formula I as set forth in claim 1, where X is chlorinein the 7-position, Y is oxygen and R¹ is OM, where M is a metal of maingroup 1 or 2 of the Periodic Table, hydrogen or C₁ -C₈ -alkyl. 8.3,7-Dichloro-quinoline-8-carboxylic acid. 9.3,7-Dichloro-8cyano-quinoline.
 10. A herbicide containing inertadditives and, as active ingredient, a dichloro-quinoline derivative ofthe formula I as set forth in claim
 4. 11. A herbicide containing inertadditives and, as active ingredient, a dichloro-quinoline derivative ofthe formula I, where X is chlorine in the 7-position, Y is oxygen, twohydrogen atoms or ═N--A--B, where A is a direct bond and B is a phenylor pyridine radical which is unsubstituted or substituted by chlorine,nitro, methyl, trifluoromethyl or methoxy, and R¹ is hydrogen, --NR² R³,where R² and R³ are identical or different and each is hydrogen, C₁ -C₆-alkyl, C₁ -C₆ -alkenyl, C₁ -C₆ -hydroxyalkyl, formyl, cyclohexyl,phenyl or pyridinyl, or R¹ is OM, where M is a metal of main group 1 or2 of the Periodic Table, hydrogen, C₁ -C₈ -alkyl, phenyl which isunsubstituted or substituted by halogen, nitro, C₁ -C₄ -alkyl ortrihalomethyl.